Alkyl phenol sulphonates



Y 35 used Patented June 25, 1940 Parson OFFICE r 2,205,946 ALKYL PnENoL sULPnoNA'rEs Lawrence H.

Flett, Hamburg, N.

Y., aslignor to National Aniline & Chemical Company, Inc.,

New York, N. Y.,

No Drawing.

Application a corporation of New York September 2c, 1933,- Serial No. 691,081. Renewed October 25, 1939 25 Claims. (01.260-512) This invention relates to a new class of alkyl phenol sulphonic acid compounds. It relates more particularly to alkyl phenol sulphonic acid compounds in which a long open-chain alkyl group 5 is directly linked to a carbon atom of the phenol nucleus.

The alkyl phenol sulphonic acid compounds of the present invention comprise the compounds which correspond with the general formula in which A represents hydrogen or a methyl group, R. represents a nuclear alkyl hydrocarbon chain (saturated or unsaturated) containing 12 or more (preferably 12 to 23, and especially 14 to 19) carbon atoms, and M represents hydrogen or a metal, particularly an alkali metal, ammonium, or an organic ammonium radical.

The said alkyl phenol sulphonic acid compounds may be used instead of the usual soaps for scour- 26 ing, cleaning, washing and toilet purposes as well as for other purposes for which ordinary soaps have heretofore been employed.

The use of the ordinary soaps (alkali metal salts of higher fatty acids) for laundry and 80 toilet purposes, as well as in various textile treating processes, is circumscribed by the fact that the ordinary soaps possess a number of properties which are undesirable. Thus they form precipitates or scums and do not lather readily when with hard water, sea-water, or solutions containing calcium and/or magnesium compounds, and when used in acid solutions; textile materials, and especially woolen goods, washed with ordinary soaps have a harsh feel; further- 40 more, in view of the relatively low solubility of ordinary soaps, the washed goods must be repeatedly rinsed in order to remove residual soap. Ordinary soaps also have the disadvantage, being salts of strong bases with weak acids, of reacting alkaline in water solution, which is objectionable from the standpoint of their use in the washing of certain fine fabrics, such as delicate silks, and in connection with their use as toilet soaps. The alkyl phenol sulphonic acid compounds may also be employed in conjunction with ordinary soaps,

since they serve to prevent objectionable precipitates from forming in hard water or in acid treating baths or in salt baths. They have thefurther advantages of being in general better wetting I agents and more soluble than the usual soaps, and

.tives of phenol (hydroxy benzene) of leaving the washed asmuch as the water solutions of said alkyl phenol sulphonic acid compounds in the form of their alkali metal salts are neutral in reaction, the latter may be safely used for the washing of delicate silks and other fine fabrics as well as for personal toilet purposes. In addition to their usefulness as detergents, the alkyl phenol sulphonic acid compounds herein disclosed may be employed, either in the form of the free acids or their salts, as wetting, impregnating, dispersing, assisting and penetrating agents.

The said sulphonic acid compounds are derivaand of the cresols (1.2- 1.3-, and 1.4-methyl-hydroxy-benzene) in which the alkyl hydrocarbon chain repgoods with a soft feel. In-

resented by R in the foregoing formula is directly linked to a nuclear carbon atom (probably para to the hydroxyl group in the case of phenol and orthoand meta-cresols) and in which the sulphonic acid group is-also directly linked to a nuclear carbon atom. For convenience they will be hereinafter referred to as alkyl phenol sulphonates" which term generically includes the phenol and cresol derivatives, whether in the form of the free acids or the salts. The preferred alkyl phenol sulphonates are those in which the alkyl group contains a branched carbon chain, whether linked to the benzene nucleus by an end carbon atom (an alpha carbon atom) or an intermediate carbon atom (that I, is, whether a primary, secondary or tertiary alkyl group). As used herein,

' the expression branched carbon chain includes secondary allwl groups of the type CHK a) in which n is 10 or more.

The alkyl phenol sulphonates of the present l prepared in various ways. Ac-

invention may be an alkyl cording to one method of preparation, phenol or cresol of the type in the presence orabsence of a 86 B. sulphuric acid, sulphuric acid monohydrate. oleum), chlorsulphonic acid, etc. As solvents or diluent there may be employed any inert organic liquid which is not readily sulphonated such as halogenated hydrocarbons of the aliphatic and aromatic series, as for example, carbon tetrachloride, dichlorethane, tetraehlorethane, dichlorbenzene, etc. When an inert solvent or diluent is used, it may be separated from the alkaline aqueous solution of the sulphonic acid salt of the alkyl phenol which results upon diluting the sulphonation mass with water and neutralizing or it may be separated in the process of drying said salt. As sulphonation assistants there may be employed the lower organic acids and/or their anhydrides, as for example, acetic acid, acetic anhydride, etc.

The sulphonation may be carried out with the aid of heating or cooling, as required, depending upon the ease of sulphonation of the alkyl phenol or cresol and the sulphonating power of the sulphonating agents. The sulphonation of the alkyl phenol or cresol may be carried out to an extent such that mainly one, or more or less than one, sulphonic acid group is present in the final product (based on the alkyl phenol compound), it depending upon the properties desired of the final product, as will appear more fully hereinafter.

The alkyl phenol sulphonates may be employed in the form of their free sulphonic acids or in the form of salts of metals (as for example, of the alkali metals) or of organic bases, or of ammonia, etc. The salts may be obtained in any suitable manner; for example by reacting the sulphonated product, either in the crude form resulting from the sulphonation or in a purified form, with a metal oxide or hydroxide, ammonia or an organic base, or of a. suitable salt of one of these, in an amount adapted to form a neutral product. Among the bases, oxides and salts which may be combined with the sulphonated products to produce salts are, for example, sodium, potassium and ammonium hydroxides; sodium, potassium and ammonium carbonates and bicarbonates; ammonia; magnesium oxide; ethylamine; pyridine; triethanolamine; propanolamines; butanolamines; diamino propanol; ethylenediamine; triethylene tetramine; etc.

The reaction mixtures resulting from the sulphonation of the alkyl phenol or cresol may also be directly employed for the formation of mixed products, as for example mixtures of salts of the alkyl phenol sulphonic acid and other acids present in said reaction mixtures, which mixtures of salts are also useful as such in accordance with the present invention. Thus, the sulphonation reaction mixture resulting from the treatment of the alkyl phenol or cresol with an amount of sulphonating agent in excess of that theoretically required to effect the desired degree of sulphonation may be treated with a suitable inorganic or organic base or basic salt (as for example, one of those mentioned) and the resulting mixture of the salt of the sulphonated alkyl phenol or cresol and the inorganicysalt (as for example, sodium sulphate) may be jointly isolated from the reaction mixture and employed as such. If it is desired to produce from such mixtures a salt of the sulphonated alkyl phenol or cresol in a form substantially free from inorganic salts (for example, inorganic sulphates) this may be accomplished by taking advantage of the solubility of the salts of the sulphonated products in alcohol and other organic solvents. Thus a mixture of a salt of the sulphonated product and an inorganic sulphate may be extracted with alcohol, and the resulting extract may be evaporated to leave a residue of the purified salt of the sulphonated product.

The sulphonated products in the form of metallic salts or salts of inorganic bases are usually yellowish to white, friable solids; and in the form of salts of organic bases vary from viscous oils to semi-solids to solids. In general, the salts are readily soluble in water and in aqueous (neutral, acid or alkaline) solutions to form solutions which are faintly colored brown or yellow, which are of a soapy nature and which foam readily. Certain of the salts, such as the salts of the aromatic monoamines and the aliphatic and aromatic polyamines, are oils which generally are insoluble in water but soluble in organic solvents (as for example, benzene, gasoline, etc.) and in aqueous solutions of alkalis (presumably by conversion to the salts of the alkalis).

It is to be understood that the invention includes products containing a plurality of alkyl phenol sulphonic acid nuclei linked together through the sulphonic acid groups by a polyvalent metal or organic basic radical, as well as products in which an alkyl phenol sulphonic acid is linked through the sulphonic acid group to a difi'erent acid compound by a polyvalent metal or organic basic radical.

Thus the invention comprehends compounds of the type X-ZX' and X-ZY, wherein X and X each represent the radical which may be the same or difierent, Z represents a polyvalent metal or organic base, Y represents a radical containing an acid group, and A and R have the meaning defined above. Examples of such types of compounds are X-Mg-X X-NH3-CH2CH2--NH3X X-NHa-CHzCHz-NHa-OSOzR,

and

NHr-CHgCHg-NHg-C mcm-nm-cmcm-mh wherein X and R have the meaning defined above, and W represents a radical containing an acid group at least one of which is a radical of the type represented by X.

The sulphonates may be dried in any suitable manner; as for example in pans in shelf, at-- bases are dried under vacuum conditions.

The invention will be illustrated by the following specific examples. It will be realized by those skilled in the art that the invention is not limited thereto, however, except as indicated in the appended patent claims. The parts are by weight.

Preparation of alkyl phenols Example 1.-Equal parts of solid cetyl alcohol and anhydrous phenol are melted and mixed together. An amount of powdered anhydrous zinc chloride equal in weight to the cetyl alcohol is then added and the whole mass is refluxed for 16 to 20 hours with suflicient agitation to keep the zinc chloride insuspension, the temperature during the refluxing varying between 175 and 185 C. The condensation reaction mass is cooled and allowed to stand sufilcientlyto set and'settle the zinc chloride, the oily layer (crude cetyl phenol) is decanted and washed with onethird of its weight of hot water (80 to C.) to decompose any zinc chloride complex or double salts. Any emulsion iormed'during the washing is broken by the additionoi small quantities of sodium chloride. The washed oil is separated from water by stratiflcation and is then distilled under a vacuum" to purify it. The fraction boiling at 190 to 225 C. at 4 mm. pressure is separately collected and represents the purified cetyl phenol. It is particularly adapted for the forma-, tion of a detergent by the conversion to a sulphonated derivative. The residue boiling above 225 C. under 4 mm. pressure represents a product which, while not satisfactory for sulphoriation to produce a detergent, may be sulphonated to produce a product useful as an emulsifying and/or insecticidal agent.

Example 2.- parts of commercial cetyl alcohol (containing 30 to 40 per cent oi! normal cetyl alcohol, 30 to 40 per cent of higher alcohols than cetyl, about 10 per cent of normal lauryl alcohol and about 20 per cent of normal myristyl alcohol) 100 parts of phenol, and 100 parts anhydrous zinc chloride are heated at to C., under a reflux condenser, with agitation for 16 hours or until condensation is practically complete.

The condensation product is washed with water until practically free from water soluble products. The resulting oil is fractionally distilled in vacuo. The fraction of the distillate which is collected between 195 C. and 240 C. at 15 mm. pressure of mercury is a faint yellow to water-white oil consisting chiefly of a mixture of alkyl phenols having the probable formula:

CH OH ical having the formula:

CmH21, C12H25, C14H29 0i CieHaa the compound in which Rm is Cid-Ian predominating, with a small amount o'f-normal alkyl phenols and some ortho isomers probably present. Y

Example 3.-100 parts of commercial cetyl alcohol, 100 parts p-cresol and 100 parts anhydrous zinc chloride are refluxed as in Example 2 for 5 hours and the product is recovered by washing the resulting oil with dilute hydrochloric acid and fractionally distillingthe washed oil in vacuo. The fraction of the distillate which is collected between 202 to 218 C. at 3 mm. pressure consists chiefly of a mixture of alkyl cresols in which the predominating compound is a secondary cetyl p-cresol.

Example 4.-Meta-cresol is employed instead of p-cresol in the process of Example 3 and the reaction mixture is refluxed for 6 hours. The product is recovered after washing with dilute hydrochloric acid by fractionally distilling in vacuo. The fraction of the distillate which is collected at 208 to 228 C. at 5 mm. pressure consists chiefly of a mixture oi! alkyl cresols-in which the predominating compound is a secondary cetyl m-cresol.

is fractionall y distilled in vacuo.

Example 5.-An admixture of 50 grams of cetene (obtained by pyrolysis of spermacetti), 50 grams of phenol and 50 grams of fused, powdered zinc chloride is refluxed and agitated for 16 hours.

' The reaction mass is washed with water and fractionally distilled. The fraction boiling between 238 to 252 C. at 13 mm. is separately collected and consists of an impure cetyl phenol. It is a white oil, insoluble in water and has a specific gravity less than 1.

Example 6.100 parts of commercial lauryl I alcohol (obtained by hydrogenation of fatty acids from cocoanut oil), 100 parts of phenol, and 100 parts of anhydrous zinc chloride are mixed and refluxed at 190 to 200 C. with agitation for about 16 hours. The condensation product is washed with water until practically free of water-soluble products, and the resulting oil is fractionally distilled in vacuo. The fraction of the distillate collected as a faint yellow to water-white oil between 210 to 230 C. at 13 mm. mercury pressure consists chiefly of lauryl (dodecyl phenols of which the probable formula of the principal constituent is l v /CHOOH CH1 Example 7.-100 parts of octadecyl alcohol (stearyl alcohol), 100 parts of phenol, and 100 parts of anhydrous zinc chloride are mixed and refluxed for about 16 hours. The condensation product is washed with water till practically free of water-soluble products and the resulting oil The fraction of the distillate collected between 235 to 270 C. at 14 mm. mercury pressure comprises chiefly paraoctadecyl phenol having the probable formula CHl mixed with a small amount of normal octadecyl phenol and probably small amounts of the corresponding ortho isomers.

Example 8.-A mixture of 50 grams of phenol, 50 grams of 1.2-heptadecene, and 25 grams of anyhdrous zinc chloride is heated with stirring at 90 to 120 C. for 15 hours. The resulting reaction massds washed with water and then subjected to fractional distillation. Theportion boiling between 220 and 270 C. at 15 mm. is separately collected. It is a colorless, or nearly so, oil consisting mostly of heptadecyl phenol.

If 1.5 grams of anydrous aluminum chloride are used in place of the 25 grams of zinc chloride in this example, and the mixture is refluxed for '8 hours, the yield and quality of heptadecyl phenol are somewhat inferior. By carrying out the condensation in the presence of 10 grams of concentrated sulphuric acid at 6 to 12 C., in place of aluminum chloride or zinc chloride, washing and distilling the resulting product and collecting the fraction distilling between 220 and 270 C., heptadecyl phenol is also obtained.

Example 9.-700 parts of an olefine with a boiling point ranging from 237 to 262 C. and having an average carbon content of 14 to 15 carbon atoms (and obtained by caustic soda treatment of the monochlor hydrocarbon separated by fractionation from the products resulting from chlorination of petroleum distillates which boil at approximately 250 C. at atmospheric pressure), 700 parts of phenol, and 350 parts of zinc chloride are mixed and heated together while agitated under reflux condenser at a temperature around 180 to 190 C. for from 5 to.16 hours. The condensed mass is diluted and washed with water until reasonably free of water-soluble impurities, and the crude brownish oil is distilled under vacuo. The distillate between 195 C. and 240 C. at 15 mm. pressure is collected. It is a faintly colored to water white oil, insoluble in water and dilute caustic soda. The product is chiefly an alkylated phenol with an average of about 14 to 15 carbon atoms in the alkyl (substituent) group.

Example 10.100 parts of commercial lauryl alcohol (obtained by hydrogenation of fatty acids derived from cocoa-nut oil and containing capryl, decyl, lauryl, myristyl, cetyl and stearyl alcohols), 100 parts of ortho cresol and 100 parts of anhydrous zinc chloride are mixed and refluxed at 190 to 200 C. with agitation for about 16 hours. The condensation product is washed with water until practically free of water-soluble products, and the resulting oil is fractionally distilled in vacuo. The fraction of the distillate collected between 215 C. and 230 C. at 13 mm. pressure of mercury is a faint yellow to water white oil and consists of a mixture of alkyl substituted ortho cresols of which the principal components have the probable formula:

' in which ALK is a straight alkyl chain of the formula C4Ha, Cal-I13, CaHir, C1oH21, CiaHas, C14H2o or CisH33. The average molecular weight corresponds with a product in which the chain represented by ALK has approximately the formula CH21.

Example 11 .--Cresylic acid (a commercial mixture of eresols) is substituted for the ortho-cresol of Example 10.

The fraction of the distillate boiling between 215-240 C. at 13 mm. mercury pressure is separately collected. It is a faint yellow to waterwhite oil comprising a mixture of alkyl derivatives of ortho-, meta, and para-cresol.

Preparation of sulphonation products of alkyl phenols Example 12.-100 parts by weight of the alkyl phenol obtained in accordance with Example 9, and having a boiling point ranging from 195 to 240 C. at 15 mm. pressure, are mixed with 148 parts by weightof sulfuric acid monohydrate at C., then heated to 70-75 C. and held there.

until a sample is completely soluble in water and in neutral, acid or alkaline aqueous solutions, and does not precipitate calcium salts from a soluble calcium salt solution containing the equivalent of 0.224 gram calcium oxide per liter. The sulphonation mix is poured into water, diluted to a final volume of 450 to 600 parts, and made neutral (for example, to delta paper, Congo paper, brilliant yellow, or brom-cresol-blue) with alkali, for example, caustic soda, or potash or their equivalents. The neutral solution is evaporated to dryness. If desired, the neutral solution can be clarified by filtration before being evaporated to dryness.

The product thus obtained (which will hereinafter be referred to as a tetradecyl phenol sulphonate) is a mixture of which the chief components are alkyl phenol sulphonates having the probable formula:

where R0 represents a branched-chain aliphatic hydrocarbon group containing mainly 14 and 15 carbon atoms, M represents an alkali metal or equivalent derived from the base used for neutralization, and p is 1 or 2 but mainly 1.

In the form of the alkali metal and alkaline earth metal salts it is a faintly colored light brown to white, friable solid, readily reduced to a comminuted or powdery form (resembling powdered soap) and readily soluble in water.

The alkali metal, alkaline earth metal, and ammonium salts of the alkyl phenol sulfonic acid are solids; the-salts derived from organic bases, e. g. ethylamine, pyridine, etc., are solids or liquids. Their aqueous solutions foam readily and behave like soaps. They do not precipitate lime from aqueous solutions of soluble calcium salts; they behave like tanning agents in that they precipitate glue and gelatin from acid aqueous solutions; they are soluble in acid, neutral and alkaline, alcoholic or aqueous solutions; and they are strong hydrotropic substances, that is, possessing the quality of efiecting solution in water of water-insoluble liquids and solids.

Example 13.-The sulfuric acid monohydrate in Example 12 is substituted by 200 parts of 66 B. sulfuric acid which is fed slowly to the agitated alkyl phenol at a temperature of -70 C. The mixture is slowly heated to 90-100 C. and held at this temperature for one hour, or until a sample is completely soluble in water and does not precipitate calcium salts (as in Example 12). The sulphonation mixture is diluted with 1750 parts of denatured alcohol, and neutralized with solid soda ash (NazCOa). The mixture is filtered and the filtrate evaporated to dryness to obtain the sodium salt of the alkyl phenol sulphonic acid practicallyfreefrom salts of inorganic acids. The resulting product is similar to that obtained in Example 12 but it does not contain the inorganic salts present in that product, and it is soluble in benzene, alcohol and other organic solvents and the solutions are useful as a detergent. In water solution it is preferably employed as a detergent in admixture with salts or other electrolyte.

Example 14.100 parts of the alkyl phenol employed in Example 12 are mixed slowly with 50 parts of chlorsulphonic acid, and the mix is heated to 70-90 C. until evolution of hydrochloric acid practically ceases and a sample of the sulphonation mass is completely soluble in water and does-not precipitate calcium salts (as in Example 12). The sulphonation mass is then diluted with water, neutralized with alkali, filtered and evaporated to dryness, etc., as in Example 12. The resulting product is similar to that obtained in Example 12.

Example 15.--100 parts of the alkyl phenol used in Example 12 are mixed with 24 parts of acetic ahhydride, and while the mass is agitated, 132 parts of 26% oleum are added slowly, so that the temperature of the mix does not exceed 50 C. Thereafter, the temperature is slowly raised to -95 C. and held there until a sample of solution is'clarified by filtration,

the sulphonation mass is soluble in water and does not precipitate calcium salts. The sulphonation. mass is diluted with water to approximately 450 .to 600 parts and neutralized with alkali. The if necessary, and evaporated to dryness. The product is similar to that obtained in Example 12.

Example 16.To 100- parts of the alkyl phenol used in Example 12, while being agitated, 64

parts of 65% oleum are added slowly. The temperature during addition of oleum is held at 30 C. while the finishing temperature is not allowed to exceed 45 in water, and does not precipitate calcium salts. The sulphonation mass is diluted, neutralized, filtered and evaporated to dryness as described in previous examples. The neutralized solution of the sulphonic acid may be treated with such an amount of alcohol that the resulting alcohol solution in water contains more than 50% alcohol. The solution is filtered to remove precipitated impurities which are mostly inorganic salts, and the filtrate containing the sulphonate is evaporated to dryness to yield the dry sulphonate practically free from inorganic salts. The product, which is similar to that obtained in Example 13, is suitable for use in organic solvents as a cleaning composition and is an excellent emulsifier. It can be used as a detergent in aqueous solutions but forbest results an electrolyte is preferably employed in conjunction therewith.

Instead ofadding alcohol to the dilution mass, the dry. crude sulphonate may bedissolved in a small amount of water, the solution repeatedly extracted with alcohol, and the alcohol extracts combined, filtered and evaporated to dryness.

Example 17.--To 30 parts of purified cetyl phenol (obtained, for example, in accordance with the procedureof Example 1) 36 parts by weight of 100% sulphuric acid are added with sufilcient agitation to insure thorough mixing without aerating the mass; the temperature of the mass being maintained below 50 C., and the sulphuric acid being added gradually (over a period of about 5 minutes) so as to avoid exceeding this temperature. The mass is further agitated while preventing the temperature from exceeding 50 C. until the desired sulphonation has been attained (for example, for an additional period of a half hour). For production of a product which does not cause precipitation of lime salts and which forms a clear solution in dilute acid solutions, the sulphonation is carried to an extent such that a 0.5 gram sample of the sulphonation reaction mixture-.dissolved in 30 cc. of distilled water with the aid of stirring and gentle heating, followed by neutralization with sodium hydroxide solution until the solution reacts faintly acid to Congo red test paper, remains clear upon addition of 220 cc. of distilled water, and furthermore, when 1 cc. of a 10% CaClz solution is added to the resulting diluted solution, the precipitate which forms disappears upon stirring, leaving a clear solution. Upon completion of the sulphonation, the sulphonation reaction mixture is poured with stirring into 2'75 parts of water containing 23 parts of sodium hydroxide, the addition being sufilciently gradual to avoid rise in the temperature of the resulting solution above 60 C. There is thus obtained sodium cetyl phenol sulphonate in an aqueous solution containing sodium sulphate in a condried on an atmospheric C. The sulphonation is' complete when a sample is completely soluble tration of the resulting. solution may be adjusted to the desired value by'suitable acidification or treatment with alkali. The resulting solution is rotary drum drier heated with steam at 40 to 50 pounds pressure, the product being scraped from the rolls in a granular or powdered form. In order to avoid corrosion of the drying rolls, the product is preferably dried in a slightly alkaline condition. The product may also be dried in shallow .pans or trays in a vacuum drier at temperatures not exceeding 100 C.

Example 18.-100 parts of purified hexadecyl (cetyl). phenol,-obtained, for example in accordance with the procedure of Example 2, 40 parts of acetic anhydride, and 160 parts of sulphuric acid monohydrate are mixed together and warmed gently to 'l0-75 C. until the product is completely soluble in water-and does not pre-' cipitate 'calcium salts froma calcium chloride or other soluble calcium salt solution containing the equivalent of 0.224 gram calcium oxide per liter. The mass is diluted with water to a final volume of 450 to 600 parts and neutralized with alkali, as for example, caustic soda or caustic potash or their equivalents. The neutral solution is clarified, if desired, by filtration, and evaporated to dryness. The product is a brown to white solid soluble in water to give brown to water-white solutions, and soluble in alcohol, benzene and other organic solvents. vIt comprises a mixture of an inorganic sulphate (e. g.,

detergent properties but having valuable insecticidal and emulsifying properties is obtained.

Example 19.'I'he neutralized solution of hexadecyl phenol sulphonic acid prepared in Example 18 or the equivalent aqueous solution prepared from the final dry sulphonates, is diluted with an equal volume of commercial denatured alcohol. thoroughly mixed for several hours, filtered and'evaporated to dryness; or the dry sulphonates are extracted with successive portions of denatured alcohol, the total amount of alcohol used for this, extraction being limited to approximately four times the weight of the dry unextracted sulphonate, the combined extracts are mixed and digested with a small amount of animal charcoal, filtered and evaporated to dryness. The residue obtained in either case is a hexadecyl phenol sulphonate "practically free from salts of mineral acids. By adding a small amount of alkali before evaporation, a white,

friable solid having a soap-like appearance and whichiis readily soluble in water is obtained.

Example 20.-- pa'rtsof octadecyl phenol (obtained, for example, in accordance with Example "7)., 20 parts of acetic anhydride and '70 parts oil- 26% oleum are mixed slowly at 40 C. and gently warmed to a temperature of 80 C. until a sample is completely soluble in water and does not precipitate calcium salts from a solution'oilcalcium chloride (or other soluble calcium salt solution) containing the equivalent of 0.224 grams calcium oxide per liter. The mass is diluted, neutralized and finished as described in Example 18.

Example 21.-100 parts penta, decyl phenol (which is made by condensing phenol with the and commercial penta decyl alcohol, having the probable formula:

CrHv Can! /CH.CHI.CH CIBII OHIOH and obtained by condensing 3 mol equivalents of amyl alcohol) is treated with a mixture of 142 parts of 100% sulphuric acid and 37 parts of 66 IB. sulphuric acid, keeping the mixture agitated at about 95 C. The mix is stirred at this temperature for about 15 minutes or until a sample is soluble in water and does not precipitate more than a trace of calcium salts from a calcium chloride solution equivalent to approximately 0.224 grams calcium oxide per liter.

The mass is diluted with water, neutralized with soda ash, filtered and evaporated to dryness.

The mass may be diluted with 80% alcohol to a volume of approximately 500 volume parts, neutralized with caustic soda, filtered and evaporated to dryness to obtain a product comparatively free from salts of inorganic acids. The resulting product is a penta decyi phenol sulphonate.

Example 22.To 100 parts of an alkyl phenol obtained by condensing phenol with an olefine of boiling range 232 to 255 C. (and derived from chlorinated petroleum distillates of about the same boiling range), as per methods described hereinbefore, 64 parts of 65% oleum are added at such a rate that the temperature of the mixture does not exceed C. The temperature thereafter is raised to to 45 C. and held at that point till a sample of the sulphonation mass is completely soluble in water and does not precipitate calcium salts.

The mass is diluted with water, and the resulting solution is neutralized with caustic soda, filtered and evaporated to dryness. Or, the solution or final product may be extracted with alcohol of greater strength than 50% and the extract evaporated to dryness to yield an alkyl phenol sulphonate practically free from inorganic.

salts, as described in Examples 13 and 19 above. The resulting product is chiefly an alkyl phenol sulphonate in which the alkyl group contains about 14 to 15 carbon atoms but averages somewhat lower than the product of Example 12.

Example 23.100 parts of tricosanol phenol, obtained by condensing tricosanol-7 in which C16H33 and CsHra are straight-chain alkyl groups) with phenol, are treated with 222 parts of 66 B. sulphuric acid at 95 C. with agitation and held at that temperature for about one hour, or until a sample is soluble in water anddoes not precipitate lime salts. The product is diluted, neutralized with caustic soda, filtered, evaporated to dryness, and, if desired, is further purified as described in previous examples. It comprises a secondary-alkyl phenol sulphonate containing 23 carbon atoms in a branched alkyl chain.

Example 24.-To 100 parts of a mixture of alkyl phenols (obtained by condensing phenol with a mixture of alcohols comprising mainly cetyl alcohol and dimethyl penta-decyl carbinol, and resulting from treatment of 1 mol equivalent of cetyl palmitate with approximately 2 mol equivalents of methyl magnesium bromide -Grignard reagentand subsequent hydrolysis), 64 parts of of 65% oleum are added while the mixture is agitated and the temperature is held under 30 C. After oleum addition is complete, temperature is raised to C. and held there until a sample of the sulphonation mixture is soluble in water and does not cause appreciable precipitation of calcium salts; about one hour at 40 C. is usually sumclent. The mix is diluted neutralized with caustic soda, filtered and. dried in the usual manner. The diluted sulphonate solution or the dry sulphonate may be treated with alcohol (to precipitate salts of inorganic acids) and a small 4 and the isoalkyl group is chiefly CuHn Example 25.A mixture of alkyl phenols is made by condensing phenol with the tertiary alcohols resulting from hydrolysis of the reaction product between the isobutyl esters of the fatty acids in cocoanut oil and the Grignardreagent, amyl magnesium bromide. The tertiary alcohols are chiefly (C5H11):.C.(OH).R where Rq=C2Hl9 to Crime. 100 parts of this mixture of alkylated phenols are treated with 64 parts of 65% oleum at 30 C. The mixture is thoroughly agitated; the temperature is permitted to rise to 50 C. and held there until a sample oi the sulphonation mixture is soluble in water and does not precipitate calcium salt as described in tests in previous examples (about 1 hour). The sulphonation mixture is then diluted, neutralized with caustic soda, filtered (alcohol-treated and decolorized, if desired), and evaporated to dryness. The product is a mixture of tertiary alkyl phenol sulphonates in which the substituent alkyl groups may be represented by the formula l ll C Hu in which R =CoH1s to CHI-11s.

Emmple 26.A mixture of alkyl phenols is prepared by condensing phenol with an oleiine having a boiling range of 160 to 235 C. at 15 mm. (which can be made by chlori'nating a petroleum distillate and converting the chlorinated product to olefine by the usual method of removing the 1101 from the molecule). The olefine contains about 15 to 23 carbon atoms.

100 parts of this mixture are mixed under agitation with 148 parts of sulphuric acid monohydrate at about 30 C. The sulphonation mixture is warmed to 65 C. and held there until a sample of the mixture is soluble in water and does not precipitate calcium salts from an aqueous solution (about 3 hours). The mixture is diluted, neutralized with caustic soda, filtered and dried. It may be extracted with alcohol and decolorized as described in previous examples.

The product is a mixture of alkyl phenol sulphonates in which the substituent alkyl groups contain from 15 to 2-3 carbon atoms.

Example 27..-20 parts of acetic anhydride are mixed with 100 parts by weight of para normal cetyl phenol (which is prepared by condensing palmitic acid into phenol and reducing the corvto the alcoholic extract before drying.

responding palmityl phenol; or by condensing palmityl chloride with benzene, reducing the corketone, sulphonating and fusing the sulphonic acid with caustic alkali in the usual manner; or by condensing n-cetyl alpha-halide with benzene, sulphonating, and fusing the sulphonic acid with caustic alkali in the usual manner; or by fractional distillation of the condensation reaction mixture resulting from the interaction of phenol, cetyl alcohol and zinc chloridecf Example 1- and recovery of the small amount of normal cetyl phenol produced as a by-product) To this agitated mixture, '75 parts of 25% oleum are added at such a rate that the temperature of the mix does not exceed 50 C.- The mix is warmed to 85 C. and held at this temperature until a sample is completely soluble in neutral, acid and alkaline aqueous solutions, and does not precipitate any calcium salts from a solution of a soluble calcium salt containing the equivalent of 0.224 gram calcium oxide per liter; When the sulphonation is completed, the reaction mass is diluted with water to 450 to 600 parts and neutralized with alkali; as for example, caustic soda, potash, soda ash, etc., or their equivalents. The neutral solution is clarified, if desired, by filtration and the solution or filtrate is evaporated to dryness.

The sulphonate thus obtained may be represented in the form of the free acid by the probable formula C1sHa3.CeH3.(OH) .SOsH or more particularly as CHi(CH:)uC HQOH Example 28.--The neutralized solution of normal cetyl phenol sulphonic acid prepared in Example 2'! (or the equivalent aqueous solution prepared from the dry sulphonate) is diluted with an equal volume of denaturedalcohol, thoroughly mixed for several hours, a decolorlzing charcoal is added, and the solution is filtered and evaporated to dryness. Alternatively the dry product resulting from the process of Example 27 may be extracted with successive portions of denatured alcohol, the total amount of alcohol used for this extraction being limited to approximately four times the weight of the dry unextracted sulphonate, the combined extracts are mixed with a small amount of animal charcoal, filtered and evaporated to dryness. The residue obtained in either case is n-cetyl phenol sulphonate practically free from inorganic salts of mineral acids.

It is preferable to If the crude product before extraction is dark colored, the purified sulphonate is lighter in color. The product dissolves very readily in neutral, acid and alkaline aqueous solutions.

Example 29.--l00 parts of the mixed normal alkyl phenols, obtained by condensing phenol with the mixture of free acids produced by saponifying cocoanut fat to form the mixed ketone phenols and reducing the ketone phenols by the well known Clemmenson method to the normal alkyl hydride are mixed, and to parts of 26% oleum are that the temperature 01 the mix does not exceed 50 C. The mix is heated to 80 C. and held at this temperature until the desired degree of sulphonation has been attained. The mass is dithis agitated mixture added at such a rate pound' then may add a small amount of alkali containing straightphenols, and 20 parts of acetic an-v luted with water, neutralized, filtered and evaporated to dryness.

The sulphonate product thus obtained comprises, chiefly, a mixture of normal alkyl phenol sulphonates in which the alkyl groups consist of straight (normal) saturated aliphatic chains containing mainly from 12 to 18 carbon atoms. In thetorm of the free acids the latter may be represented bythe following general probable formula a. on

in which R= a normal alkyl group from Cal-I25 to C1aH37, inclusive.

It will be realized by those skilled in the art that changes may be made in the products, and in the processes of preparing them, hereinbefore described, without departing from the scope of, the-invention.

Thus, the sulphonated alkyl phenols may be prepared in various ways from various intermediates; for example, phenol, ortho-, meta-, or para-cresol, or their mixtures may be condensed with an alkylating agent adapted to substitute an alkyl group containing at least 12 carbon atoms in the aromatic nucleus, and the resulting combe sulphonated; or an alkyl ether of phenol or cresol in which an alkyl group containing at least 12 carbon atoms is linked by an oxygen atom to the aromatic nucleus, may be rearranged to the alkyl phenol and sulphonated before or after the rearrangement; or benzene or toluene or their sulphonic acids may be condensed with an alkylating agent adapted to substitute an alkyl group containing at least 12 carbon atoms in the aromatic nucleus, followed by sulphonation to substitute one or more sulphonic aromatic nucleus (it not alcorresponding phenol sulphonic acid compound,

and, if necessary,-the product may be sulphonated; or the alkyl group may be substituted in the aromatic nucleus in the form of a ketone by condensing benzene, toluene, phenol, or a cresol, with'a fatty acid or acid chloride corresponding with the desired alkyl group, in place of an alykylating agent in the process just enumerated, and subsequently reducing the resulting ketone at any stage of the process.

In the condensation of phenol or a cresol with an alkylating agent there may be employed as alkylating agents non-aromatic alcohols (as for example, straight-chain, primary monohydric alcohols; straight-chain, secondary monohydric alcohols;

etc.), olefine hydrocarbons or branched-chains, and containing a double bond preferably between the ultimate and penultimate carbon atoms; and halogen derivatives of hydrocarbons; ing at least'12 carbon atoms and preferably 12 to 23 carbon atoms in an alkyl hydrocarbon chain. A preferred alkylating agent is commercial cetyl alcohol containing a mixture of normal alcohols, including a major proportion of cetyl alcohol together with lauryl alcohol, myristyl alcohol and alcohols higher than cetyl.

As condensing agents theremay be employed anhydrous zinc chloride, anhydrous aluminum chloride, anhydrous antimonic chloride, anhycohols of all types;

branched-chain primary alcohols; branched-chain secondary alcohols; tertiary al-' all containdrous ferric chloride, zinc, sulphuric acid (66 B6 monohydrate, oleum), etc. The particular condensing agent to be employed varies somewhat with the alkylating agent employed. Preferably the proportion of alkylating agent employed with respect to the phenol is such that not more than two alkyl radicals of the type represented by R in the foregoing formula, and preferably only one of said alkylradicals, is contained in the resulting alkyl phenol. Thus, at least mols of phenol per mol of alkylating agent is preferably employed in the condensation. A ratio as low as 1 to 1 may be employed, but the yield of the resulting alkyl phenol containing one long alkyl groupwill be less. Further the amount of condensing agent employed may vary over a wide range. For example, in using zinc chloride as the condensing agent, much less of it is generally required in condensing an alkyl chloride with the phenol or cresol than when an alcohol is condensed therewith; in general, a long-chain alcohol (as for example, lauryl or cetyl alcohol) requires about an equal weight of,zinc chloride for best results, whereas a chlorinated long-chain hydrocarbon requires only about 5 to 10 per cent of its weight of zinc chloride.

The time during which the condensation reaction of the alkylating agent and phenol may be 'carried out also may be varied and will depend on the nature of the alkylating agent. In general the condensation between an alcohol and phenol or a cresol is practically complete within about 3 to about 5 hours, at refluxing temperature, but the quality of the product appears to be improved by continuing the heating for a longer period of time, apparently to rearrange alkyl ethers present to alkyl phenols, as disclosed and claimed in copending application of Jack D. Robinson, Serial No. 42,358, filed Sep-- tember 26, 1935. The condensation of an alley] chloride with phenol or a cresol is satisfactorily complete in about 1 hour at refluxing temperature or in about 3 to 6 hours at 135 C., but is also continued for a longer time for best results in preparing a detergent. With zinc chloride as the condensing agent, the period of heating may be extended to 16 hours or more without seriously harming the quality or decreasing the yield of the alkyl phenol.

The crude alkyl phenol resulting from the condensation is preferably purified, as for example, by fractional distillation and collecting a middle fraction having in general a boiling point range of not more than C., and the purified compound is preferably employed for. sulphonation to produce a detergent in view of the resulting superior detergent properties. Distillation is preferably carried out at a pressure not exceeding mm. to avoid decomposition.

As has been indicated above, in sulphonating the alkyl phenol, an inert solvent and/or a sulphonation assistant may or may not be used. The temperature at which the sulphonation is carried out may vary within wide limits. For example, temperatures as low as about 0 C. and as high as about 140 C. may be employed. In general the more vigorous the sulphonating agent the lower is the preferred temperature. Ordinarily the completion-of the sulphonation is carried out at a temperature in the neighborhood of about 70 to about 80 C. The ratio of sulphonating agent employed with respect to the alkyl phenol also may be varied. While the preferred amounts are given in the above examples, an

amount of sulphuric acid or other sulphonating agent equivalent to from 1 to about 5 parts by weight of sulphuric acid monohydrate per part by weight of the alkyl phenol may be employed. The extent to which the sulphonation is carried out may vary with the individual material being sulphonated and the use to be made of the sulphonated product. In general the extent of sulphonation of the alkyl phenol treated is such as to form chiefly the monosuiphonic acid of the alkyl phenol, and to sulphonate impurities as well, it present. In some cases, a degree of sulphonation which corresponds with a product having maximum detergent properties is not completely soluble in water to form a clear solution and/or may cause some precipitation of lime salts. (An aqueous solution of calcium chloride containing the equivalent of 0.224 gram of calcium oxide per liter of solution is merely-employed in the above examples as a representative hard water solution for test purposes. It is to be noted that the invention is in no respect limited thereto.)

It is to be noted that in using the sulphonated products mixtures of two or more of the sulphonated products hereinbefore referred to may be employed. Furthermore, any of the said sulphonated products or their mixtures may be employed in connection with other hydrotropic substances; dispersing, emulsifying and/or penetrating agents; aliphatic or aromatic sulphonic acids; acid alkyl esters of sulphuric acid; sulphonation products of petroleum oil; alkyl aryl sulphonates free from a nuclear hydroxyl group; and/or their derivatives. In addition to the above described uses of the l sulphonated products of the present invention and in recapitulation of the various uses hereinbefore described for said products, it is noted that the said sulphonated products may be employed for a large variety of purposes wherein cleansing, dispersing, penetrating, wetting, tanning, surface tension lowering, and similar action is required.

Thus the said sulphonic acids and their salts may be incorporated into compositions containing laundry and toilet soaps, water insoluble dyes, sulphurized oils, hydrocarbons, alcohols, esters, alkyl amines, mixed amines, fats, oils, waxes, unguents, alkyl phenols, ketones, mineral oils, resinous substances, alkyl sulphates, organic acids of an aromatic or aliphatic nature, inorganic bases, organic bases, inorganic salts, inorganic acids, etc. i

The said sulphonates are of great value where dispersion is required, including emulsification, suspension, colloidal solution, conversion into foam (aeration), reduction of surface tension effects, as well as detergency. The said sulphonated products are of particular value in treating natural or artificial fibrous substances such as cotton, wool, silk, hair, straw or any other animal or vegetable fiber, artificial silks, rayon, hides, skins, leather, paper, feather etc.; for example in dyeing with water-soluble or water-insoluble dyes, the presence in the dye-containing composition of alkyl phenol sulphonate products causes the dyestuif to be well dispersed in, and imparts great penetrating power to the treating composition containing the dye, whereby levelling, brilliancyandfastnesscharacteristics of the shade of the dye, as well as penetration of the dye into the fiber, are enhanced.

Because of their hydrotropic nature, the said sulphonlc acids and their salts are valuable ingredients of compositions in which solids and liquids which are insoluble or almost insoluble in impregnating;

water are desired to be held in solution or colloidal suspension or are desired to be solubilized.

The said sulphonates can be incorporated, in compositions prepared and applied with any kind of dye or mixture of dyes, as for example, acid, basic, chrome, developing, direct, sulphur or vat dyes, or aniline black, or the so-called "ice colors," etc. They may be used in baths or preparations of any kind and use for dyeing, printing, padding, stencilling, stamping, developing or coloring fibrous material in any manner whatsoever. The compositions can be employed in baths or preparations containing dispersed or solubilized water-insoluble dyes and can be applied, for example, to fibrous material made of or containing artificial silk.

In the treatment of fibrous material, compositions containing these sulphonates can be applied to increase penetration of treating solutions into the fiber and such improvement of penetrating power is had regardless of the alkaline, neutral or acid nature of the solution, and is effective in all manner of processes, such as bowking, bleaching, cleaning, carbonizing, degreasing, dry-cleaning, felting, finishing, greasing, impregnating, lubricating, lathering, laundering, mercerizing, softening, stripping, scouring, sizing, washing and wetting. In acid treating baths, as for example, in wool carbonizing baths or acid-dyeing baths, the said sulphonates act as anti-acid and acid-protective agents. Their detergent properties in acid solution permit, for example, scouring of raw wool in an acid carbonizing'bath.

The said sulphonates appear to react with silk and protect it, as' for example, against staining by cotton dyes.

The said sulphonates further have the valuable property of imparting excellent, and often unusually intensive, dispersing, emulsityin'g and penetrating characteristics to compositions containing them, which thereby become valuable ac tive agents in processes for the removal of grease, wax, soap deposits, etc.; in processes for cleansing, scouring, bowking, degreasing; or in processes requiring the rapid transfer of active agents into the fiber (such as acid in carbonizing; dye or intermediate solutions and dispersions in dyeing, padding, printing, etc.; latex solution in caustic soda in mercerizing; hypochlorite in bleaching; hydrosulphite in stripping; etc.)

Compositions containing the said sulphonates for finishing, lubricating, sizing, and soaping fibrous material are effective and rapid in action. They inhibit the deposition'of insoluble soaps in baths which contain hard water and soaps, and sometimes completely prevent precipitation of lime soaps.

The said sulphonates may also be employed to permit more uniform precipitation of artificial silk in a precipitating bath, better washing of nitrocellulose in a steeping and washing bath, more uniform lubrication of threads by a spinning bath, and greater cleansing with a dry cleaning bath. Fibrous materials impregnated with a solution of the said sulphonates have a marked, increased imbibing or absorption power for the varied treating solutions and compositons commonly applied to such material.

The said sulphonates can be incorporated and applied in tanning compositions alone or in combination with other tanning and/or treating compositions for leather, skins, etc.

' substances such as vat blanc-fixe, soot, minerals, etc., and in the making aqueous solution in frothing qualities.

Their dispersing power makes them valuable ingredients for making aqueous compositions comprising dispersions of pigments, insoluble dyes, colloidal sulphur,

of pigments, inks, plastics, etc. The dispersions may be made in any desirable manner; as by adding the solid, in friable or flnely divided form, to a dilute or concentrated solution of the said sulphonates; or the sulphonates may be incorporated with the solid, before addition to aqueous media; or the insoluble substance may be caused to form in the composition in the presence of the sulphonates, as for example, by mixing an organic soluble dye and an appropriate metal salt solution to form a lake pigment in an aqueous medium, or by precipitating a basic dye or dyes from an the presence of the sulphonates in the solutions.

The said sulphonates are valuable ingredientsin electrolytic baths inducing by their presence more uniformdepositions from electrolytes.

The said sulphonates are also valuable stabilizing agents for diazonium and nitroso preparations, and. prevent their rapid decomposition. They combine readily with diazo preparations of this type to precipitate stable compounds capable of being dried and handled without fear of rapid decomposition. They are accordingly valuable ingredients in compositions containing diazonium or nitroso preparations applied to fibrous materials by dyeing, printing, padding and generally related processes.

The said sulphonates possess the valuable property of dispersing gases in liquids, thereby imparting to their solutions strong foaming and They are valuable components of compositions and processes requiring frothing or foaming, as for example, in dyeing textile materials by foam methods; in protecting oxidizable baths (e. g., reduced dye baths) against oxidation by air; in the separation of minerals by flotation; in aerating liquids and washing of gases; and in fire extinguishing preparations.

The emulsifying, dispersing and wetting Dower imparted to compositions containing the said sulphonates makes them valuable components of cosmetic preparations such as hair washes, dentiirices, cleansers, toilet soaps, mouth washes; as well as of germicides, insecticides, fungicides, parasiticides, etc., in which preparations they cause emulsification and uniform dispersion of active ingredients, andv impart strong penetrating and wetting properties which insure intimate contact with surfaces to which the preparations are applied. For the same reasons, they are valuable ingredients of oils applied as boring oils, lubricants, etc. for products such as leather, or tor spinning processes, or for machinery; and of aerated liquids or compositions for holding and The said sulphonates also possess the property of altering ultra violet light in the direction of the visible spectrum. Accordingly, they can be incorporated in compositions, particularly in organic solvents in which they are soluble, to be applied for the purpose of preventing sunburn, or other objectionable action of ultra violet light. They may be applied to convert ultra violet light to visible light, and thus serve as dyes or pigments for substances to be viewed under ultra violet light.

The said sulphonates, by their power to impart reduced surface tension to compositions containing them, are valuable agents in processes for breaking oil emulsions.

The free sulplionic acids are effective and valuable fat-saponifying agents.

The said sulphonates may also be employed as intermediates for the preparation of other chemical compounds. Inasmuch as they contain a phenolic hydroxyl group they may be employed as coupling components for azo dyes.

Compositions containing these sulphonates in solution are not confined to such as are made with and contain water as the essential liquid medium. Water is preferred, but may be replaced by a1- cohol or other solvent as required or found desirable and in which the sulphonate is soluble.

In addition to their use as intermediates for the production of sulphonated products, the alkylated phenols andcresols may be employed as detergents in the form of solutions in alcoholwater mixtures containing caustic alkali; as insecticides, germicides, parasiticides, or vermicides; as wetting agents in conjunction with emulsifying agents; as assistants in emulsiflcation; as solvents; as intermediates for the production of resins of all kinds in which phenols are reacted with resin-forming ingredients of various types; as plasticizers for resinous products, cellulose plastics, and other synthetic and natural plastics of all types; as intermediates for the production of azo dyestuffs useful for the dyeing of cellulose esters and ethers, and/or soluble in organic solvents; as inhibitors of gum formation in gasoline (for example, tetradecyl pyrogallol and related alkyl polyhydric phenols); etc.

It will be understood that} in general, the alkyl phenol sulphonates of the present invention difler from each other with respect-to their wetting, emulsifying, detergent and other properties, and that these properties are more or less altered and/or differently affected by the presence therewith of inorganic salts and other products and/or impurities. For example, the detergent powers of onealkyl phenol sulphonate may be relatively greater than that of another alkyl phenol sulphonate while the wetting powers are less and the presence of sodium sulphate may affect or alter the detergent powers or properties more than it does the wetting properties. It is evident, therefore, that in the uses of the alkyl phenol sulphonates, these differences in properties should be takeh ordinarily into account provided comparable results are to be obtained.

The compounds of the present application are claimed generically in my copending application Serial No. 691,082, filed of even date herewith. Methods of making the alkyl phenol compounds and their sulphonates, certain of the alkyl phenols and sulphonates, and certain uses thereof, disclosed in the present application, are claimed in one or more of my copending applications Serial No. 737,777, filed July 31, 1934; Serial Nos. 42,155, 42,156 (Patent 2,133,287, issued October 18,

1938), 42,157, 42,158 (Patent 2,134,711, issued November 1, 1938), 42,159 (Patent 2,134,712, issued November 1, 1938), 42,162, 42163 (Patent 2,133,288, issued October 18, 1938), and 42,164

flied September 25, 1935; Serial Nos. 93,718 and 93,719. led July 31, 1938; and Serial No. 186,733, filed January 24, 1938.

I claim:

1. An alkyi phenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R represents an alkyl hydrocarbon chain containing 12 to 23 carbon atoms and A represents a member of the group consisting of hydrogen and the methyl radical.

3. An alkyl phenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R represents an alkyl hydrocarbon chain containing 12 to 23 carbon atoms.

4. A mixture of a plurality of alkyl phenol sulphonates which in the form of the free sulphonic acids correspond with the general formula in which R presents an alkyl hydrocarbon chain containing 10 to 16 carbon atoms.

5. A mixture of a plurality of alkyl phenol sulphonates which in the form of the free sulphonic acids correspond with the general formula group consisting of hy- 6.,An alkyl phenol sulphonate which in the form of the free sulphonic acid. corresponds with thegeneral formula.

"R- Born in which R represents an alkyl hydrocarbon radical containing at least 12 carbon atoms in a branched carbon chain and A represents a member of the group consisting of hydrogen and the methyl radical.

7. An alkyl phenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R represents an alkvl hydrocarbon chain containing 14 to 19 carbon atoms and A represents a member of the group consisting of hydrogen and the methyl radical.

8. An alkyl phenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R. represents an alkyl hydrocarbon radical containing 14 to 19 carbon atoms in a branched carbon chain.

9. A mixture of a plurality of alkyl phenol sulphonates which in the form of the free sulphonic acids correspond with the formula 3- son:

in which R. represents an alkyl hydrocarbon radical containing at least 12 carbon atoms, at

least one of said alkyl phenolsulphonates containing 14 to 19 carbon atoms in a branched carbon chain in the radical represented by R.

11. A mixture of a plurality of alkyl phenol consisting of 1 sulphonates which, in the form of the free sulphonic acids, correspond with the formula BOIH in which It represents an alkyl hydrocarbon radical containing at least 12 carbon atoms and A represents a member of the group consisting of hydrogen and the methyl radical, the alkyl groups represented by B. being derived from the mixture of alcohols obtained by reducing the fatty acids of coconut 0 a,

12. An alkyl phenol sulphonatewhich in the form of the free sulphonic acid corresponds with the general formula A.- a-crrin which R represents a straight chain alkyl hydrocarbon radical containing at least 10 carbon atoms and-A represents a member of the group consisting of hydrogen and the methyl radical.

13. An aikylphenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R. represents a straight chain alkyl hydrocarbon radical containing 10 to 18 carbon atoms.

14. An alkyl phenol sulphonate which in the form of the free sulphonic acid corresponds with the general formula in which R represents an alkyl hydrocarbon radical containing 14' to 15 carbon atoms in a branched carbon chain derived from an olefine hydrocarbon, being in the form of the sodium salt a friable solid soluble in water.

15. A sodium salt of an alkyl phenol sulphonic acid which salt corresponds with the general formula R- SOrNa in which R represents an alkyl hydrocarbon chain containing at least 12 carbon atoms and A represents a member of the group consisting of hydrogen and the methyl radical.

16. A sodium salt of an alkyl phenol sulphonic acid which salt corresponds with the general formula.

o in which R represents a straight chain alkyl hydrocarbon radical containing at least carbon atoms and A represents a member 01 the group consisting of hydrogen and the methyl radical.

17. A sodium salt of an alkyl phenol sulphonic acid which salt corresponds with the general formula CH: in which R represents a straight chain alkyi hydrocarbon'radical containing 10 to 16 carbon atoms.

18. Sodium cetyl phenol sulphonate, corresponding with the formula being a yellowish to white friable solid soluble in water and in organic solvents.

19. A mixture of a plurality of sodium salts of alkyl phenol sulphonates corresponding with the formula in which R, represents an alkyl hydrocarbon radical containing 10 to 16 carbon atoms, the alkyl radicals represented by R being derived from a mixture 01' alcohols obtained from a natural product.

20. Sodium dodecyl phenol sulphonate, corresponding to the formula CHKCHQoCH- R- son?! in which R represents a saturated alkyl hydrocarbon chain containing 12 to 18 carbon atoms. 24. Compounds having the following general formula N on R SOrNa in which R. represents a saturated alkyl hydrocarbon chain containing 12 to 18 carbon atoms.

25. sulphonated dodecyl hydroxy benzene.

LAWRENCE H. FLETT. 

